Sprayable and aerosolizable webforming compositions

ABSTRACT

THERE ARE DISCLOSED SPARYABLE AND AEROSOLIZABLE WEBFORMING COMPOSITIONS FOR FORMING SELF-SUPPORTING, THREE DIMENSIONAL WEBS OF RANDOMLY ASSOCIATED, JOINED MONOFILAMENTS RANGING IN AVERAGE DIAMETER FROM ABOUT 1 TO 10 MICRONS, THE SPRAYABLE WEB-FORMING COMPOSITIONS COMPRISING A WATER-INSOLUBLE HYDROCARBON ELASTOMER, AT LEAST ONE WATER:INSOLUBLE RESIN OF HYDROGENATED ROSINS AND POLYOL ESTERS THEREOF, PHENOLIC RESINS, HYDROCARBON RESINS OR COUMARONE-INDENE RESINS COMPARTIBLE WITH SAID ELASTOMER, AND SOLVENT COMPARTIBLE WITH SAID ELASTOMER AND SAID RESIN, AND THE AEROSOLIZABLE WEB-FORMING COMPOSITION COMPRISING, IN ADDITION TO THE COMPONENTS STATED FOR THE SPRAYABLE WEB-FORMING COMPOSITIONS, A PROPELLANT INERT TO SAID ELASTOMER, RESIN AND SOLVENT. THE SPRAYABLE AND AEROSOLIZABLE WEB-FORMING COMPOSITIONS MAY CONTAIN ENCAPSULATED COMPONENTS, E.G., COLORING AGENTS, PERFUMES OR OTHER SCENTS, E.G., INSECT SEX ATTRACTANTS, AGRICULTURAL CHEMCALS, INSECTICIDES, ECT. A PLASTICIZER CAN BE INCLUDED IN THE AEROSLIZABLE FORMULATION TO IMPART INCREASED TACKINESS TO THE WEB OVER EXTENDED TIME PERIODS. THE WEB-FORMING POLYMER SOLUTIONS OR DISPERSIONS CAN BE DISPENSED FROM VARIOUS TYPES OF DISPENSING SYSTEMS AND EQUIPMENT, E.G. FROM SPARY GUNS, PORTABLE AEROSOL CANS, ECT. TO PROVIDE AN ADVANTAGEOUS WAY OF DISPENSING AGRICULTURAL TREATING AGENTS OR OTHER ENCAPSULATED MATERIALS ONTO PLANTS OR OTHER DESIRED REPOSITORIES OR LOCATIONS WITHOUT INTERFERING THEREWITH, E.G. WITH PLANT GROWTH OR METABOLIC PROCESSES THEREOF.

3,791,983 SPRAYABLE AND AEROSOLIZABLE WEB- FORMING COMPOSITIONS TheodoreMaierson, Dayton, Ohio, assignor to The National Cash Register Company,Dayton, Ohio No Drawing. Continuation-impart of abandoned applicationSer. No. 659,857, Aug. 11, 1967. This application Apr. 22, 1968, Ser.No. 723,285

Int. Cl. 1301 13/02; C08d 9/12; C09k 3/30 US. Cl. 252-305 11 ClaimsABSTRACT OF THE DISCLOSURE There are disclosed sprayable andaerosolizable webforming compositions for forming self-supporting, threedimensional webs of randomly associated, joined monofilaments ranging inaverage diameter from about 1 to 10 microns, the sprayable web-formingcompositions comprising a water-insoluble hydrocarbon elastomer, atleast one water-insoluble resin of hydrogenated rosins and polyol estersthereof, phenolic resins, hydrocarbon resins or coumarone-indene resinscompatible With said elastomer, and solvent compatible with saidelastomer and said resin, and the aerosolizable web-forming compositioncomprising, in addition to the components stated for the sprayableweb-forming compositions, a propellant inert to said elastomer, resinand solvent. The sprayable and aerosolizable web-forming compositionsmay contain encapsulated components, e.g., coloring agents, perfumes orother scents, e.g., insect sex attractants, agricultural chemicals,insecticides, etc. A plasticizer can be included in the aerosolizableformulation to impart increased tackiness to the web over extended timeperiods. The web-forming polymer solutions or dispersions can bedispensed from various types of dispensing systems and equipment, e.g.from spray guns, portable aerosol cans, etc. to provide an advantageousway of dispensing agricultural treating agents or other encapsulatedmaterials onto plants or other desired repositories or locations withoutinterfering therewith, e.g. with plant growth or metabolic processesthereof.

This application is a continuation of my copending application Ser. No.659,857 filed on Aug. 11, 1967, now abandoned.

While the invention is described in detail hereinbelow primarily interms of its agricultural use, it will be realized that the webs andmonofilaments containing encapsulated components can be used for a widevariety of purposes, e.g., to disseminate encapsulated shark repellentor other chemicals onto water; to deliver sea dye marker to desiredareas of use in the water; to aid in police investigation and detectionWork (both in the fields of overt and covert area intrusion); in thearts, e.g., theatrical arts, to simulate spiderwebs; in other specialtyproduct use areas, e.g., to trap and immobilize insects, especiallyflies, mosquitoes, etc. The present invention can be used whenever it isdesired to deliver encapsulated components and adhere them at leasttemporarily.

One of the vexatious problems encountered in treating agriculturalproducts to prevent insect and other pests from devouring plant life isthat of the effective life of the treating agent, i.e., insecticide orpesticide, dispensed thereon. Thus, it is a relatively simple matter tospray plant life with insecticides, e.g., by aerial spraying, but thespraying must be repeated frequently due to the fact that theinsecticide can volatilize into the open air. Frequently plant life issprayed with insecticidal solutions and the solvent evaporates taking aportion of the insecticide along during the evaporation. Another probleminvolves the atmospheric deletion effect upon the insecticide, e.g., theeffects that rain and Wind have in removing the in- United States Patentice secticides from the plant. Still another problem exists inmaintaining liquid treating agents on the desired portion, e.g., leavesdue to run-off, viz., the downward gravitational migration of the liquidinsecticide from the leaves and upper plant parts to the earth. Thus itwill be realized that often large portions of the agricultural treatingagent applied to plant life never actually remains on the plant for asufiicient period of time to accomplish the purpose for which it wasapplied thereto.

One attempt to partially solve this problem involves spraying the plantwith an organic polymer solution containing the agricultural treatingagent. The polymer solution, being sticky at the time of application,enhances the adherence of the treating agent to the plant leaves andother parts so that the insecticide remains on the desired situs of use.This procedure is far from satisfactory, however, because the polymericfilm frequently upsets or interferes with the plants metabolism, e.g.,does not allow the plant leaves and other parts to breathe. Thisinability of the plant to carry out its normal metabolism frequentlyresults in stunted growth, other releterious side effects, or even deathof the plant.

The present invention offers an effective and eflicient solution to mostof the above indicated problems by providing for adherence ofencapsulated treating agent(s) to the desired situs of use because thepolymeric web, being tacky at the time of application to said situs,adheres thereto. Since the web is composed of tacky monofilaments andcontains the encapsulated component, the encapsulated component isdeposited upon the adherent to said situs without interfering withnormal plant metabolism. Moreover, those portions of the web notactually adhered still retain the encapsulated material in the immediatevicinity because these web portions become mechanically interlocked inthe leaves, stems and other plant parts due in part to the threedimensional or nonplanar web configuration. In short, the encapsulatedagricultural treating agents are placed in a condition where they areretained more efficiently by the plant life and can therefore serve tocombat insects and other pests present in the locality of the plants.Also, the present invention allows the use of delayed releaseagricultural treating formulations which can permeate gradually throughthe capsule walls to be available to combat insects and pests in thearea of the plant to which the webs containing the encapsulated treatingagents have been applied.

According to one facet of a preferred embodiment of this invention, thepolymeric webs containing the encapsulated component can be applieddirectly to an individual bush or plant structure by delivery from anaerosol container, e.g., conventional portable aerosol hardware (can),by an unskilled applier, e.g., the average home gardener. Thus, it willbe apparent that the present invention has the added advantage offlexibility in systems and ways of delivery of the desired encapsulatedcomponents depending upon the economics involved, area to be treated andthe intended end use of the encapsulated component. For example, when itis desired to treat a large field of plants; instead of delivering theweb from aerosol cans, the encapsulated agricultural or other agent canbe sprayed using substantially conventional aerial spraying hardware tospread the polymeric, three-dimensional spider webs over a wide areahomogeneously. Since the webs are light in Weight yet areself-supporting at the time of their formation and deposition and forvarying periods thereafter (depending more or less upon the specificpolymeric materials used to formulate the Web-forming composition); theycan be sprayed from relatively low flying aircraft in the manner inwhich present insecticidal compositions (unencapsulated) are applied ina hit or miss manner.

The three-dimensional web configuration formed of adherent,interconnected randomly associated monofilaments is especiallyadvantageous in situations where it is desired to get rid of insectswithout using harmful chemical poisons. For example, the aerosolizable,web-forming polymeric formulation can contain encapsulated orunencapsulated insect sex attractants. The insect then crawls or fliesinto the three-dimensional web and is substantially retained therein dueto the tackiness and interconnected structure of the web itself. Forexample, house flies and mosquitoes have been effectively immoiblizedand retained on such three-dimensional, polymeric artificial spiderwebs. The web, itself, without additional components is quite useful forthis purpose and can be made tacky for extended periods by use oftackifying plasticizers.

WEB-FORMING COMPOSITIONS Any water-insoluble, web-forming polymericcomposition can be employed provided that it forms a web ofself-supporting monofilaments capable of spanning a distance of at leastone inch and preferably three inches or more. A wide variety ofwater-insoluble polymeric compositions are suitable for this purpose.They can be employed in the form of organic solutions or dispersions orin any other form so long as they can be dispensed from suitableapparatus to form the subject webs.

Suitable exemplary types of and specific rubber or elastomeric polymericmaterials that can be used include, but are not limited to, thefollowing: homopolymeric polybutadienes having number average molecularweights ranging from about 2,400 to about 3,000, e.g., Buton 150 acommercially available polybutadiene (Enjay Chemical Company) containingchiefly (65 weight percent) the 1,2-butadiene adduct with some residualvinyl unsaturation; natural rubbers having number average molecularweights ranging from about 1,000 to 4,000, e.g., cis-1,4-polyisoprenes;NBR rubbers, viz., nitrile-butadiene rubbers having number averagemolecular weights ranging from about 900 to about 4,500, e.g.,1,3-butadieneacrylonitrile copolymers; SBR rubbers, viz.,styrenebutadiene rubbers having molecular weights of about 900 to about4,500, e.g., styrene-1,3-butadiene copolymers containing 20 to 80 weightpercent l,3-butadiene; halogenated rubbers, esp. chlorinated rubbers,such as, neoprene rubbers having molecular weights of about 800 to about5,000, e.g., homopolymeric polychloroprenes; polyalkylene homopolymershaving molecular Weights ranging from about 8,000 to about 200,000,especially homopolymeric polybutenes and polyisobutylenes such asVistanex M'ML 140 a commercially available polyisobutylene having amolecular weight (Staudinger) ranging from about 117,000 to about135,000 (Enjay Chemical Company), Vistanex MML 100 a commerciallyavailable polyiso butylene having a molecular weight ranging from about81,000 to about 99,000 (Enjay Chemical Company), Vistanex LM-MS acommercially available polyisobutylene having a molecular weight ofabout 8,700 to about 10,000 (Enjay Chemical Company), Vistanex 200 acommercially available polyisobutylene having a molecular weight ofapproximately 200,000 (Enjay Chemical Company); trans-polyisoprenehomopolymers, e.g., Trans PIP, a commercially available precipitatedbalata (naturally occurring) rubber (Polymer Corporation Limited);cis-1,4-polyisoprenes having molecular weights of about 2,000 to about50,000, e.g., Natsyn 400 a commercially available cis-1,4-plyisoprenehomopolymeric synthetic rubber (The Goodyear Tire & Rubber Company);hydrocarbon terpolymers containing ethylene, propylene and anon-conjugated or conjugated diene comonomer, e.g., Nordel, acommercially available, sulfur-curable terpolymer of ethylene, propyleneand 1,4- hexadiene (E. I. du Pont de Nemours & Co.) and Royalene acommercially available hydrocarbon terpolymer of ethylene, propylene anda non-conjugated C to C diene (United States Ru b r 3 Usually it isdesirable to employ a compatible webforming blend of a hydrocarbon orhalogenated hydrocarbon elastomer and at least one resin, natural orsynthetic. Suitable exemplary resins which can be used include, but arenot limited to, the following types of and specific resinous material:hydrogenated rosins and various polyol esters of hydrogenated rosins,e.g., Staybelite Resin a commercially available hydrogenated rosinhaving a softening point of 68 C. (A.S.T.M. Ring & Ball), an Acid Numberof 165, a Saponification Number of 167, a Refractive Index of 1.5008 anda density of 1.045 (Hercules Chemical Co.), Staybelite 10 a commerciallyavailable glycerol ester of hydrogenated rosin having a softening pointof 84 C. (Hercules Drop Method), an Acid Number of 7, an Index ofRefraction of 1.532 and a specific gravity of 1.07 at 25 C./25 C.(Hercules Chemical Co.), refined highly hydrogenated rosin, e.g., ForalAX" a commercially available hydrogenated rosin having a softening pointof 75 C. (Hercules Drop Method), an Acid Number of 160, a RefractiveIndex of 1.4955 and containing 0.15 weight percent abietic acid asdetermined by conventional ultraviolet analysis; phenolic resins, e.g..Durez 19900 a commercially available phenolformaldehyde resin having asoftening point of 900 C. (A.S.T.M. Ball & Ring) and a specific gravityof 0.960 at 25 C./4 C. (Hooker Chemical Corp); hydrocarbon resins, e.g.,Wing Tack a commercially available hydrocarbon resin having a softeningpoint of 95 C., an Acid Number of less than 1.0, an Iodine Number of anda specific gravity of 0.93 (The Goodyear Tire & Rubber Co.); terpenehydrocarbon resins, e.g., Piccolyte S- a commercially available terpenehydrocarbon resin having a softening point of 115 C. (A.S.T.M. Ball &Ring), a specific gravity of 0.97, an Iodine Number of 8, a RefractiveIndex of 1.53 and an Acid Number (maximum) of less than 1 (PennsylvaniaIndustrial Chemical Corp); petroleum hydrocarbon resins, e.g., Piccopale100 SF a commercially available petroleum hydrocarbon resin having asoftening point of 100 C. (A.S.T.M. Ball & Ring), a specific gravity of0.97, an Iodine Number of 60, a Refractive Index of 1.53, an Acid Numberof less than 1 and a Saponification Number of less than 1 (PennsylvaniaIndustrial Chemical Corp.); aromatic hydrocarbon resins, e.g., Nevchem100 a commercially available highly aromatic hydrocarbon resin having asoftening point of 100 C. (A.S.T.M. Ball & Ring), a specific gravity of1.07 at 25 C., an Iodine Number of 62, an Acid Number of less than 1 anda Refractive Index of 1.59; and coumarone-indene resins, especiallyphenol-modified coumarone-indene resins.

According to a preferred embodiment of this invention, it has beendiscovered that excellent web-forming, aerosolizable compositions can beprepared by using plasticized or unplasticized mixtures of one or moreelastomers with a compatible resin, e.g., a polyisobutylene having amolecular weight of 117,000 to 135,000 (Vistanex MML with a hydrogenatedrosin (Staybelite Resin) and including as an optional, but preferred,hydrocarbon terpolymer elastomer component a curable terpolymer ofethylene, propylene and a C to C nonconjugated or conjugated dienepolymer, e.g., Nordel.

COMPATIBLE SOLVENTS A wide variety of solvents can be employed todissolve the web-forming polymer material(s) in accordance with thisinvention. Of course, the selection of the given solvent or solventsystem (mixture of individual solvents and components) will be in largepart dictated by the particular polymer material(s) chosen to form theweb and the manner selected for applying it to the situs of use. Thus,e.g., when employing an aerosolizable web-forming polymer compositioncomprised of a mixture of Vistanex MML 140, Staybelite resin and Nordel;it is preferred to employ C to C hydrocarbon solvents or C ExemplaryPolymeric material Type of solvent solvent Polybutadiene- AromaticToluene. Natural rubber.-- d Hexane. Polyisobutylene Do. Ethylenepropylene terpoly-mer. do Do.

PROPELLANTS These aerosolizable and sprayable polymeric compositionsemployed to form the filaments and webs in accordance with thisinvention usually employ a propellant material, especially, whendelivered from an aerosol container. A wide variety of propellantmaterials can be used so long as the propellant material is compatiblewith not only the polymeric material(s) being used but also the solventfor said polymer(s). Also, when the web contains capsules, thepropellant material should be inert with respect to both the cell wallmaterial of the capsules (external) phase. While it is preferable thatthe propellant(s) also be inert with respect to the gaseous, liquid orsolid treating agent contained within the capsules (internal phase orencapsulated component); this is not mandatory because the cell wallseparates the propellant(s), solvent(s), etc., from the internal phasematerial(s). According to a preferred embodiment of this invention whenthe web-forming polymer material is a mixture of polyisobutylene,hydrogenated rosin and a terpolymer of ethyelne, propylene and1,4-hexadiene, using n-hexane or cyclohexane as the solvent; it ispreferred to employ halogenated hydrocarbon propellants, e.g., mixturesof Freon 11 and Freon 12. Freon 11 is trichloromonofluoromethane. Freon17 is dichlorodifluoromethane. In general, any inert propellant(s) canbe used so long as it is inert with respect to the polymer(s), resin(s),solvent(s) and capsule cell Wall material. Other satisfactorypropellants which can be used herein include, but are not limited to:vinyl chloride (VC), butane, isobutane, propane and mixtures of any twoor more of the aforementioned propellants. When the web-formingcompositions are dispensed from conventional spray guns (as contrastedwith aerosol cans) it is economically preferable to use air, nitrogen,carbon dioxide or mixtures containing one or more of them as thepropellant medium.

OPTIONAL ADDITIONAL INGREDIENTS Other adjuvant materials can be includedin the webforming compositions, such as tackifying plasticizers, e.g.,hydrogenated or nonhydrogenated C to C lower alkyl esters of organicrosin acids, e.g., hydrogenated methyl abietate; di-C to C lower alkylphthalates; mono-, diand tri-C to C alkyl phosphates, etc. Otheroptional ingredients which can be included to tailor-make theweb-forming compositions are pigments, dyes or coloring agents (to beincluded in the polymer formulation, per se, as distinct from theencapsulated component), filler materials, e.g., diatomaceous earth,bentonite clay, titanium dioxide (in powdered or particulate form), etc.

6 ENCAPSULATED COMPONENT(S) A wide variety of solid and liquid (andgaseous) materials can be encapsulated and incorporated into theselfsupporting polymer web articles of the present invention. Inconnection with the encapsulation disclosure contained herein, theexpression internal phase will be employed with reference to thosematerials which are encapsulated, whereas the term external phase isused with reference to the cell wall material, viz., the material whichconstitutes the capsule wall of the encapsulating material. Suitableexemplary internal phase materials which can be employed in accordancewith this invention include, but are not limited to, the following:pigments, dyes, inks, perfumes, adhesives, phosphorescent andfluorescent chemicals, sea dye marker, shark repellent, insecticides,insect repellants, pesticides, bacterial spores toxic to variousinsects, e.g., in the larvae stage, herbicides, rodenticides,termiticides, fungicides, bactericides, plant hormones (defoliants),insect sex attractants, etc. Of course, these materials can be used inunencapsulated form in the polymeric webs of this invention. Moreover,the above-noted and similar encapsulated materials can be dissolved ordispersed in oils and oily or oil-type materials by encapsulationprocedures known to the art, e.g., such encapsulation procedures asindicated in US. Pats. 2,712,- 507, 2,730,456, 2,730,457, 2,800,457,2,800,458 and 3,190,837. A recommended encapsulation procedure forencapsulating rodenticides and insecticides can be found in US. Pat.3,265,629, which indicates in detail in Example 5 a procedure forencapsulating sodium fiuoroacetate (rodenticide) and in Example 9thereof there is indicated a specific procedure for encapsulatingcalcium arsenate (an insecticide). Additional encapsulation procedures,both chemical and mechanical, which can 'be used to encapsulate variousmaterials for use in the polymeric webs of this invention can be foundin Microencapsulation" by Anderson et al. (Harvard M. B. A. Candidatesreport), published by Management Reports, Boston, Mass. (1963), thedisclosure of which is incorporated herein by reference.

In similar mannner a wide variety of external phase (cell wall)materials can be used to encapsulate the above-mentioned and othercomponents. Suitable exemplary encapsulating materials which can be usedin accordance with this invention include, but are not limited to, thefollowing: polyvinylidene chloride, polyethylene, ethyl cellulose,nitrocellulose, polystyrene, shellac, polyvinylalcohol, ureaformaldehydeand other aminoplast condensates, phenol-formaldehyde and other phenoliccondensates, etc.

One typical procedure which can be employed to encapsulate selectedencapsulated components, e.g., sodium fluorescene (sea dye marker),using ethyl cellulose as the capsule cell wall material is as follows:dissolve 4 weight parts (wt. pts.) of ethyl cellulose N-type (viz.,having an ethoxy content of from 49.0 to 49.3 wt. percent in 200 wt.pts. of cyclohexane. Heat to C. and add 4 wt. pts. of Epolene C 10, acommercially available low molecular weight polyethylene (EastmanChemical Products, Inc.), and 40 Wt. pts. of sodium fluorescene (finelyground) while stirring. Continue stirring and allow slow cooling to roomtemperature (approximately 20 C.). Decant all excess liquid media andwash encapsulated solids with fresh cyclohexane. Spread washed solids ontray and air dry. The encapsulated solids can then be screened toexclude any material in excess of about 50 microns (diameter).

A typical encapsulation procedure for encapsulating selectedencapsulated components using nitrocellulose (cellulose nitrate) as thecapsule cell wall material is as follows: Prepare a 4% by weightsolution of nitrocellulose in methyl ethyl ketone. Stir at 25 C. until aclear solution is obtained. With constant agitation add 16 wt. pts. ofsodium fiuorescene as a finely divided powder. While continuing thestirring at 25 C. add slowly 60 wt. pts. of

Butarez 25 a commercially available low molecular weight polybutadiene(Phillips Petroleum Co.), preheated to 50 C. Stir for an additional 15minutes to complete phase separation and wall formation. Add volumeparts of t-butyl titanate and stir for 8 to 16 hours to cross-link theethyl cellulose, thus preventing solvation by propellants. Wash withligroin, a saturated volatile fraction of petroleum boiling in the rangeof 20 to 135 C. several times to remove excess polymer. Dry underambient conditions.

Subsequent to its formation, the encapsulated component can be added tothe sprayable or aerosolizable webforming composition for dispensationthereof. One of the benefits of this invention concerning itsencapsulation embodiments is that the encapsulated components can beadded to the web-forming formulation and stored for extended periodsprior to use without adverse effects which otherwise might occur due tointimate association of the encapsulated component with the solvent(s),propellant(s), etc.

TYPICAL FORMULATION PROCEDURE (AERO- SOLIZABLE COMPOSITIONS) Thefollowing procedure illustrates a way in which liquid insecticide can bereduced to an apparent powder (encapsulated) form and subsequently bedispensed into an aerosol web-forming dispensing system. The liquidinsecticide, viz., one which is liquid at ambient temperatures, isencapsulated using the gelatin encapsulation procedure set forthhereinabove to prepare small diameter capsules in the 10 to 40 micronsize range. After spray drying the capsules appear as a free flowingpowder, yet contain the liquid insecticide.

An aerosolizable web-forming composition is then prepared by mixing 14.4grams (g.) of a 5 wt. percent solution of Vistanex MML 140 in n-hexane,7.2 g. of a 5 wt. percent solution of Nordel in n-hexane and 43.2 g.n-hexane. This mixture is then introduced into a 6 ounce aerosol canwith a 1 inch diameter opening. To this mixture is added 1 g. of 10 to40 micron capsules containing the liquid insecticide and the mixture isshaken to mix the ingredients. Air is expelled from the aerosol canusing a stream of propellant gas. Then immediately thereafter the valveassembly is crimped into the aerosol can (neck). The valve used can be acommercially available one such as No. 041250 (Precision Valve Corp.)which has a 0.030 inch diameter orifice and a dip tube extending well tothe bottom of the aerosol can. Sixty milliliters (ml) of a propellantmixture of 65 volume percent Freon 12" and 35 volume percent VC isinjected through the valve into the aerosol can. All ingredients arethen mixed by gentle shaking. An activator is then fitted on the valvestem, e.g., No. 041250 (Precision Valve Corp), to complete the assembly.This aerosol unit will now respond to finger-tip pressure applied at thetop of the applicator to deliver the web containing encapsulatedinsecticide to any desired situs of use. Of course, the same procedurecan be used to formulate aerosolizable web-forming compositionscontaining an unencapsulated agricultural treating agent component, orno such component for that matter.

The below table indicates the characteristic concentration ranges forvarious components usually present in the aerosolizable compositions.All percents stated herein are by weight unless otherwise noted.

Percent of total composition Propellant. 40 to 85. 50 to so I Activesuspended ingredient, e.g. 0.25 to 8... 0.25 to 6... 0.25 to 5.

agricultural agent.

8 TYPICAL FORMULATION PROCEDURE (SPRAYABLE COMPOSITIONS) A solventmixture of 60% MEK (methyl ethyl ketone) and 40% toluene is employed todissolve and form a mixture containing 3% Hycar 1072 and 1% Hercolyn D.Hycar 1072 is a commercially available butadiene-acrylonitrile rubbermodified to contain charboxyl groups (B. F. Goodrich Co.). It has aspecific gravity of 1.00 and a Mooney viscosity of 46 to 62. Hercolyn Dis a commercially available plasticizing resin which is a pale viscousliquid, the hydrogenated methyl ester of rosin abietic acid (HerculesPowder Co., Inc.). This mixture can be used as a sprayable base solutionin which a variety of encapsulated or unencapsulated treating agents canbe suspended. The mixture of polymers, solvent(s) and treating agent(s)is then transferred to the cup of a conventional spray gun andpressured, e.g., to from 25 to 50 pounds per square inch with nitrogen,air or other conventional pressuring media. Upon spraying, webstructures containing the treating agent(s) are produced. Pressure isadjusted to obtain optimum results, depending on the specificformulation used. The below table gives characteristic concentrationranges for components usually present in sprayable compositions.

-- Ste 10.... 41:010..-- 5to10.

Polymer(s) (elastomer(s)) Resin 0.25 to 8.-- 0.25 to 6.-- 0.25 to .5

Active suspended ingredien The invention will be illustrated in greaterdetail in the examples which follow. It should be understood that thepurpose of these examples is to illustrate the present invention.Accordingly, they should not be considered limitmg.

EXAMPLE 1 This example illustrates a typical areosolizable compositionand the formation of a self-supporting, three dimensional polymeric webtherefrom.

A polymer base formulation is prepared by dissolving ten grams ofStaybelite Resin along with 20 grams of a 10% by wt. solution ofVistanex MML- in n-hexane in 30 grams of n-hexane. To 20 grams of theabove noted polymer base formulation (placed in an aerosol can) is added15 ml. of Freon 11. After securing the valve, 30 ml. of Freon 12 isadded under pressure in the aerosol can. The above formulation was thenaerosolized onto a set of wires arranged in parallel to one another butspaced approximately 3 inches apart and located essentially in the sameplane. A self-supporting, three dimensional web structure is formed ofrandom monofilaments. The monofilaments measure from 2 to 7 microns indiameter and are arranged in random fashion adhesively attached andinterconnected to one another. In sunlight (or artificial light) thisweb closely resembles a spider web, but it is three dimensional whereasa spider web is two dimensional (usually) in a curved locus. Thethree-dimensional web, even though it contains no agricultural treatingagents or insecticide, is useful to catch and immobilize small insects,e.g., houseflies, fruitflies and mosquitoes.

EXAMPLE 2 This example illustrates the formation of a tackythreedimensional, self-supporting web similar to that of Example l, butcontaining an encapsulated component.

The formulation procedure of Example 1 is followed but using aweb-forming composition of 3.6 grams Staybelite Resin, 3.6 gramsVistanex MML-100 (5 wt. percent solution in n-hexane), 1.8 grams Nordel(5 wt. percent solution in n-hexane) and 0.5 grams of Hercolyn D(hydrogenated methyl abieta-te) dissolved in 6 grams of n-hexane. Tothis formulation is added grams of an encapsulated dye. The encapsulateddye component is a solution containing 2 wt. percent ofbenzoleucomethylene blue and 2 wt. percent of Crystal violet lactonewherein the solvent is a 5050 mixture of Magnaflux Oil and Arochlor1242. Magnaflux Oil is a commercially available high boiling refinedkerosene (Shell Chemical Co.) and Arochlor 1242 is a commerciallyavailable chlorinated biphenyl (Monsanto Co.). This internal phase isencapsulated using the following conventional gelatin encapsulationprocedure to produce capsules in the size range of 5 to 15 microns. Onehundred eighty milliliters of an aqueous gel sol containing 11 wt.percent gelatin is mixed with 180 milliliters of an aqueous gum arabicsol containing 11 wt. percent gum arabic. The gelatin employed is a highbloom strength (275 minimum) pork skin acid-extract gelatin. The aqueousgel sol and gum arabic sol are prepared and mixed at a temperature ofapproximately 55 C. Then the mixture is added to 1000 milliliters ofdistilled water (maintained at approximately 55 C.) in an appropriatesize beaker. Then 200 milliliters of the internal phase liquid(colorless dye solution) is added to the diluted gelatin-gum arabic sol.(When the internal phase is a solid, approximately 200 grams of thesolid are added.) The diluted sol containing the material to beencapsulated is stirred vigorously to adjust to the proper drop size.Then the temperature is allowed to drop gradually over a 2 to 3 hourperiod to 22-25' C. Then the temperature of the coacervate is chilled toC. After this, 10 milliliters of a 25 wt. percent aqueous glutaraldehydesolution is added to the coacervate solids to effect cross-linking ofthe gelatin cell wall material. Then the coacervate is stirred for from6 to 24 hours. Nalcoagl035, a commercially available 40 wt. percentcolloidal silica suspension (Nalco Chemical Co.) is added to thecoacervate prior to spray drying on a basis of 10 wt. percent Nalcoag1035 solids on total coacervate (encapsulated) solids. The propellant isa mixture of 35 volume percent vinyl chloride and 65 volume percentFreon 12.

This aerosolizable composition is placed in a conventional aerosol canas in Example 1. Using the same parallel wires device (3 inch gapbetween wires) a selfsupporting, three-dimensional Web is formed uponaerosolization. The monofilaments have average diameters of 2 to 7microns and are randomly associated within the tacky web structure. Uponbreakage of the capsules and release of the internal phase, thepreviously colorless dye turns blue due to reaction with the silicaovercoat. Thus the instant tacky web containing an encapsulatedcolorless dye which exhibits latent color upon capsule rupture, isuseful to indicate area intrusion (and in overt detection work ingeneral).

EXAMPLE 3 The web-forming polymer composition of Example 2 is formulatedin accordance with the procedures of Examples 1 and 2 but containing 5grams of a fluorescent solid pigment as the encapsulated component. Thepigment employed is Fluorescent Pink Pigment Velva-Glo, a commerciallyavailable pink fluorescent pigment in a urea-formaldehyde resin base(Radiant Color Co.) and the encapsulation medium is gelatin (externalphase). The propellant is VG-12 Blend, 20 mls. By encapsulating thepigment the deteriorating effect, frequently experienced in the presenceof organic hydrocarbon solvents, is minimized.

This web-forming composition is then introduced into a conventionalaerosol can as noted in Examples 1 and 2. The web is formed byactivating the can valve, and the Web is applied onto a botanicalsupport from a distance of about three feet. The web adequately supportsthe encapsulated component and the web, itself, is sufliciently tacky toadhere to said support. The web remains tacky, self-supporting andadherent for a period of at least 8 10 hours. While the encapsulatedmaterial in this example is a fluorescent pigment, it is clear thatagricultural treating agents could be present as the internal phase inthe capsule, e.g., herbicides, fungicides, insecticides, pesticides,

' etc.

EXAMPLES 4 to 23 Using the procedure of Examples 1 and 2, a variety ofinternal phase materials are formulated into the webformingaerosolizable composition of Example 2. In Example 4, unencapsulatedtitanium dioxide particles having a diameter of 1 to 10 microns areused. In Example 11, unencapsulated sodium fluorescene (see dye marker)is incorporated into the web-forming polymer formulation. In theremaining examples, the treating agent or included material isencapsulated using the below listed capsule cell wall material.

Capsule cell wall Ex. Treating agent or material material 4. TiO(decorative artificial spider web) 5..-- Chlordane (termiticide and antkiller) 1,2,4,5,6,7,- Gelatin. 8,8-octachloro-4,7-methano 3-alpha, 4,7,7alpha tetrahydroindane.

6. 2,4-D (deioliant), 2,4-dichloro phenoxy acetic acid- Do.

7---.. 2,4,5 1 (deioliant), 2,4,5-tiichloro phenoxy acetic Do.

8- PMA" (defoliant), phenylmercuric acetate Do.

9 135T (insecticide), dichlorodiphenyl trichloro- Do.

' ane.

10- Pine oil (odorant), mixture of tertiary and secondary Do. terpencalcohols, specific gravity 0927-0940, regrztgetige index 1.4780-L4820,distillation range 200- 11 Sodium fluorescene (sea dye marker) 12 2 ..doEthyl cellulose.

13.-.. Urea (plant nutrient) 0.

14--.. N N-diethyl toluimid (insect repellant) Gelatin.

15.... N,N"diethyl toluimid, 10 wt. percent solution in Do.

neutral mineral spirits.

16--.. Alpha-ethylbenzyl butyrate (sex attractant-Medi- Do.

terranean fruit fly).

17- Methyl eugenol (sex attractant-Oriental fruit fly) Do.

18.... Camphor (cat rcpellaut) Do.

. Paradichlorobenzene (dog repellent) Do.

20--.- Bone oil (dog repellent), mixture of chiefly hydro- Do.

carbons, pyridine bases and amines, specific gravity 0.9000.980.

21...- Oil of Sassafras (dog repellent), mixture of chiefly Do. safrole,eugenol, eamphor, pinene and phellandrene.

22--.. Allylisothiocyanate Do.

23.--. Bacillus thuringiensis, var. thurz'ngiemis Berliner Ethyl(pathogenicide for the European corn borer, cellulose.

Ostrim'a nubilalis (Hubner) larvae.

While the preceding examples illustrate the present invention in greatdetail, it should be understood that this invention in its broadestaspects is not necessarily limited to the specific elastomers, resins,solvents, propellants, internal phase and external phase encapsulationmaterials, encapsulation procedures, etc., present in these examples.For example, the self-supporting, three-dimensional polymeric webs cancontain a profusion (thousands to hundreds of thousands to millions andmore) of individual minute capsules (microcapsules) having diametersranging in size from 1 to microns. Usually the individual capsule havediameters of about 5 to 50 microns and preferably about 10 to 40microns. Similarly instead of the elastomer or resin being a singleelastomer or resin material, compatible mixtures of any two or more ofthe herein mentioned elastomers or resins can be employed as theelastomer and resin components, respectively. In similar manner theencapsulated component can actually be a profusion of individualcapsules which contain a plurality of internal phase materials. Hencethe webs (and monofilaments) can contain both a plurality of individualcapsules, some of which contain one internal phase material and some ofwhich contain a plurality of internal phase materials in each individualcapsule.

What is claimed is:

1. An aerosolizable, web-forming composition for formingself-supporting, three-dimensional webs of randomly associated, joinedmonofilaments ranging in average diameter from about 1 to 10 micronscomprising from about 0.2. to about 5 Wt. percent of water-insolublehydrocarbon elastomer, about 2 to about wt. percent of at least onewater-insoluble resin of hydrogenated rosins and polyol esters ofhydrogenated rosins, phenolic resins, hydrocarbon resins, orcoumarone-indene resins compatible with said elastomer, about 10 toabout 40 wt. percent of solvent compatible with said elastomer and saidresin and about 40 to about 85 wt. percent of propellant inert to saidelastomer, resin and solvent; said compatible elastomer and resinmonofilaments being selfsupporting over a span of at least one inch uponaerosolization and said wt. percents being based on total composition,wherein said composition is contained in a pressurized aerosolcontainer.

2. An aerosolizable, web-forming composition according to claim 1 whichincludes tackifying plasticizer.

3. An aerosolizable, web-forming composition according to claim 1 whichincludes from about 0.25 to about 8 wt. percent of encapsulatedcomponent, based on total composition, said encapsulated component beingpresent as individual capsules having diameters ranging from 1 to 100microns.

4. An aerosolizable, web-forming composition according to claim 3wherein said propellant and solvent are essentially inert to the cellwall material of said encapsulated component.

5. An aerosolizable, web-forming composition according to claim 3wherein said encapsulated component comprises agricultural treatingagent.

6. An aerosolizable, web-forming composition according to claim 3wherein said encapsulated component comprise colorless dye possessinglatent color.

7. An aerosolizable, web-forming composition according to claim 1wherein said hydrocarbon resins are terpene hydrocarbon resins,petroleum hydrocarbon resins or aromatic hydrocarbon resins.

8. A sprayable, web-forming composition for forming self-supportingthree-dimensional webs of randomly associated, joined monofilamentsranging in average diameter from about 1 to 10 microns comprising fromabout 3 to about 8 wt. percent of water-insoluble hydrocarbon elastomer,about 3 to about 10 wt. percent of at least one water-insoluble resin ofhydrogenated resins and polyol esters of hydrogenated rosins, phenolicresins, hydrocarbon resins, or coumarone-indene resins compatible withsaid elastomer, about to about wt. percent of solvent compatible withsaid elastomer and said resin, and from about 0.25 to about 8 wt.percent of encapsulated component, said encapsulated component beingpresent as individual capsules having diameters ranging from 1 tomicrons, said compatible elastomer-resin monofilaments beingself-supporting over a span of at least one inch upon spraying, and saidwt. percents being based on total composition.

9. A sprayable, web-forming composition according to claim 8 whereinsaid solvent is essentially inert to the cell wall material of saidencapsulated component.

10. A sprayable, web-forming composition according to claim 8 whereinsaid encapsulated component comprises agricultural treating agent.

11. A sprayable, web-forming composition according to claim 8 whereinsaid encapsulated component comprises colorless dye possessing latentcolor.

References Cited UNITED STATES PATENTS 2,349,508 5/1944 Mack 26027 X2,800,458 7/1957 Green 252-316 3,265,629 8/1966 Jensen 252-316 3,361,6791/1968 Paulus 252-305 RICHARD D. LOVERING, Primary Examiner US. Cl. X.R.

71-3, 64 A, 64 F, 70, 119; 161-174, DIG 1; 252-1, 188.3 R, 301.3 R, 364,408, 522; 26027 R, 27 BB, 29.7 B; 424-16, 45, 77, 84, 93, 352, 354

